US20230348370A1 - Process for making taurine - Google Patents
Process for making taurine Download PDFInfo
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- US20230348370A1 US20230348370A1 US18/002,329 US202118002329A US2023348370A1 US 20230348370 A1 US20230348370 A1 US 20230348370A1 US 202118002329 A US202118002329 A US 202118002329A US 2023348370 A1 US2023348370 A1 US 2023348370A1
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- taurine
- sulfonation
- aminoethanol
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- sulfate ester
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- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 title claims abstract description 215
- 229960003080 taurine Drugs 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 76
- 230000008569 process Effects 0.000 title claims abstract description 52
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 104
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 68
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 65
- -1 2-aminoethanol hydrogen sulfate ester Chemical class 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 40
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 34
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 34
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 33
- 238000005886 esterification reaction Methods 0.000 claims abstract description 31
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 29
- 230000032050 esterification Effects 0.000 claims abstract description 28
- 239000011541 reaction mixture Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 42
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 38
- 239000007921 spray Substances 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 35
- 239000011261 inert gas Substances 0.000 claims description 31
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 31
- 239000011236 particulate material Substances 0.000 claims description 29
- 239000010409 thin film Substances 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 239000007832 Na2SO4 Substances 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 2
- 238000004587 chromatography analysis Methods 0.000 claims 1
- 238000010924 continuous production Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000007789 gas Substances 0.000 description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 22
- 235000011152 sodium sulphate Nutrition 0.000 description 21
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 19
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 9
- 235000010265 sodium sulphite Nutrition 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- IVGRSQBDVIJNDA-UHFFFAOYSA-N 2-(2-aminoethylamino)ethanesulfonic acid Chemical compound NCCNCCS(O)(=O)=O IVGRSQBDVIJNDA-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 235000001014 amino acid Nutrition 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000013068 control sample Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- GWLWWNLFFNJPDP-UHFFFAOYSA-M sodium;2-aminoethanesulfonate Chemical compound [Na+].NCCS([O-])(=O)=O GWLWWNLFFNJPDP-UHFFFAOYSA-M 0.000 description 4
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 3
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000010979 pH adjustment Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FUPKJQFINJHPEG-UHFFFAOYSA-N 2-(carboxyamino)ethanesulfonic acid Chemical group OC(=O)NCCS(O)(=O)=O FUPKJQFINJHPEG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000011210 chromatographic step Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229910000856 hastalloy Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- IQGWPPQNIZBTBM-UHFFFAOYSA-N 2-aminoethanol;sulfuric acid Chemical compound NCCO.OS(O)(=O)=O IQGWPPQNIZBTBM-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010724 circulating oil Substances 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 150000004691 decahydrates Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000000378 dietary effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 229940045998 sodium isethionate Drugs 0.000 description 1
- LADXKQRVAFSPTR-UHFFFAOYSA-M sodium;2-hydroxyethanesulfonate Chemical compound [Na+].OCCS([O-])(=O)=O LADXKQRVAFSPTR-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
Definitions
- This invention relates to a continuous process for producing taurine from aminoethanol sulfate ester, also called 2-aminoethanol hydrogen sulfate ester (AES).
- aminoethanol sulfate ester also called 2-aminoethanol hydrogen sulfate ester (AES).
- Taurine also known as 2-aminoethanesulfonic acid
- Taurine is an amino acid that is found in natural dietary sources, biosynthesized in the body and is also produced by chemical synthesis for commercial purposes.
- Taurine is sometimes referred to as a conditional amino acid because it is derived from cysteine like other amino acids but lacks a carboxyl group that usually belongs to amino acids. Instead, it contains a sulfide group and can be called an amino sulfonic acid.
- the world’s annual consumption of taurine has been more than 50,000 tons, of which more than 80% are used as food and nutrition additives.
- Two methods have been used commercially to produce taurine, one method having ethylene oxide (EO) as starting material, and the other method having monoethanolamine (MEA) as starting material.
- EO ethylene oxide
- MEA monoethanolamine
- EO is reacted with sodium bisulfite to produce sodium isethionate, which is then converted via ammonolysis to sodium taurinate.
- Sodium taurinate is then neutralized to produce taurine.
- sodium taurinate is neutralized with sulfuric acid, then a mixture of taurine and sodium sulfate is obtained.
- sodium taurinate may be neutralized with sulfur dioxide to obtain taurine and to regenerate sodium bisulfite.
- taurine produced via the EO method is a powder, and tends to form a hard cake over a short period of time during storage (in a matter of weeks), possibly due to the presence of unknown impurities.
- the process also involves some serious hazards from the viewpoint of safety since it uses ethylene oxide as a raw material, and ethylene oxide has extremely strong toxicity and carcinogenicity as well as posing considerable safety risks in its transport and handling.
- the reaction from EO is carried out at very high temperatures (220-280° C.) and pressures (>100 bars).
- taurine in a conventional method using MEA as the starting material, taurine can be prepared by reacting MEA with sulfuric acid to obtain the intermediate 2-aminoethanol hydrogen sulfate ester (AES) and then sulfonating this ester intermediate.
- AES 2-aminoethanol hydrogen sulfate ester
- the MEA method uses a much safer starting material and produces a needle-shaped crystalline taurine product with excellent stability during transportation and storage as compared to the taurine powder produced in the EO method.
- a further advantage is the mild processing conditions as compared to the high temperature and pressures as required in the EO method.
- a disadvantage of the MEA method has been its higher cost of manufacture and higher capital expenditures, as compared to the EO method.
- a further disadvantage of the MEA method is the lengthy time required for the sulfonation stage, typically from 35-40 hours, due to the slow reaction of AES and sodium sulfite.
- the MEA method also typically has a low product yield in the sulfonation step.
- U.S. Pat. 9,145,359 discloses a method for the production of taurine by a cyclic process of reacting monoethanolamine, sulfuric acid, and ammonium sulfite in the presence of additives to inhibit the hydrolysis of 2-aminoethanol hydrogen sulfate ester (AES) intermediate.
- AES 2-aminoethanol hydrogen sulfate ester
- the patent states that the hydrolysis of AES is accelerated under both acidic and basic conditions, and contends that the yield of taurine can be drastically increased by strictly maintaining the pH of the reaction mixture from 6.0 to 8.0 and carrying out the sulfonation reaction at a temperature of 80 to 150° C.
- the patent discloses examples wherein starting materials were reacted in an autoclave equipped with a stirrer for 24 hours at 110° C. under autogenous pressure for 24 hours, and examples wherein starting materials were reacted in the same autoclave for 18 hours at 120° C.
- U.S. 10,131,621 has the same named inventor as U.S. 9,145,359.
- U.S. 10,131,621 discloses an extraction process for recovering aminoalcohols and glycols from aqueous streams of taurine production.
- the aqueous streams which contain aminoalcohols and/or glycols are first mixed with a base to increase pH and then extracted with C 3 -C 6 alcohols, ketones, and ethers.
- the aqueous streams are then returned to their respective cyclic process for the production of taurine.
- the patent states that according to the MEA process disclosed in U.S. Pat. No.
- Typical EO and MEA methods are both batch type processes that do not allow for continuous production of taurine.
- the present invention relates to a process for making taurine, comprising forming 2-aminoethanol hydrogen sulfate ester in a first, esterification step by reacting monoethanolamine with sulfuric acid, then sulfonating the 2-aminoethanol hydrogen sulfate ester from the first, esterification step by reaction with a sulfite, bisulfite or combination of these in the presence of carbon dioxide, a carbonate, bicarbonate or a combination of any of these in a second, sulfonation step to produce a taurine product.
- the present invention relates to a continuous process for making taurine, wherein the first, esterification step is carried out continuously with some concurrent water removal to produce a continuous 2-aminoethanol hydrogen sulfate ester feed for the second, sulfonation step, and the second, sulfonation step is also carried out directly and continuously on this 2-aminoethanol hydrogen sulfate ester feed from the first, esterification step.
- the molar ratio of the sulfite, bisulfite or combination thereof to the 2-aminoethanol hydrogen sulfate ester is equal to or greater than 1.0 and less than about 3.0, preferably less than 2.0, more preferably less than 1.8, and even more preferably less than 1.5.
- the molar ratio of the carbon dioxide. carbonate, bicarbonate or combination of any of these to the 2-aminoethanol hydrogen sulfate ester is equal to or greater than 0.1 and less than 1.0.
- a first stream, a second stream and a third stream are added to a sulfonation vessel, wherein the first stream comprises 2-aminoethanol hydrogen sulfate ester, the second stream is chosen from carbon dioxide, a carbonate, a bicarbonate or a combination of any of these, and the third stream comprises an aqueous solution of at least one of a sulfite, a bisulfite or a combination of these, and the combined first, second and third streams are subjected to heat in the presence of an inert gas such that taurine is formed.
- the concurrent water removal involved in that step will be at least in part accomplished by contact with an inert particulate material during the esterification step which possesses the capability of receiving and removing water from the process as it is formed, then in these embodiments removing the inert particulate material to provide a 2-aminoethanol hydrogen sulfate ester product for the second, sulfonation step.
- the concurrent water removal is accomplished at least in part by introduction of a feed comprising at least some monoethanolamine and at least some sulfuric acid into a spray dryer or thin film evaporator, and reacting the at least some monoethanolamine and the at least some sulfuric acid while using spray drying or thin film evaporation to remove water from the process.
- the concurrent water removal is accomplished at least in part by use of the inert particulate material with also carrying out some of the esterification within a spray dryer or thin film evaporator.
- the spray drying or thin film evaporation follows some reaction of monoethanolamine with sulfuric acid in the presence of the inert particulate material to form 2-aminoethanol hydrogen sulfate ester, while in other embodiments the reaction of monoethanolamine with sulfuric acid in the presence of the inert particulate material is carried out substantially in the spray dryer or thin film evaporator.
- the water removal accomplished in the first, esterification step by any means or combination of means will be sufficient to enable full conversion to the desired 2-aminoethanol hydrogen sulfate ester intermediate.
- FIG. 1 is a process flow diagram of a continuous taurine production process in accordance with aspects of the invention.
- FIG. 2 depicts a drying apparatus for water removal in accordance with aspects of the invention.
- FIG. 3 depicts an apparatus for sulfonation in accordance with aspects of the invention.
- FIG. 4 depicts an apparatus for sulfonation in accordance with aspects of the invention.
- FIG. 5 depicts a process flow diagram of a continuous taurine production process using carbon dioxide in the second, sulfonation step.
- FIG. 6 provides a tabulation of results from a number of Examples reported below.
- FIG. 1 is a process flow diagram of an illustrative continuous taurine production process in accordance with aspects of the invention.
- a continuous taurine manufacturing process 100 in one embodiment comprises a continuous first, esterification step 102 wherein monoethanolamine (MEA) and sulfuric acid (H 2 SO 4 ) are continuously reacted, with at least some degree of concurrent water removal.
- MEA monoethanolamine
- H 2 SO 4 sulfuric acid
- this concurrent water removal involves use of an inert particulate material that possesses the capability of receiving and removing water from the esterification step as it progresses. In other embodiments, this concurrent water removal involves carrying out some of the esterification in the course of removing water from the process by spray drying or thin film evaporation. In still other embodiments, the water removal involves both use of an inert particulate material as well as spray drying or thin film evaporation.
- this capability can be associated, for example, with a porous inert particulate material wherein the pores are such as to receive and hold water as the esterification reaction proceeds, or with a material which readily forms stable hydrates as the esterification reaction proceeds.
- the inert particulate material will also preferably be substantially insoluble in all of sulfuric acid, monoethanolamine and water under the conditions of both the esterification step and the subsequent sulfonation step, so that the material can be readily separated by from the desired taurine product following the sulfonation step.
- a particularly suitable inert particulate material having these qualities is (anhydrous) sodium sulfate, which forms a stable decahydrate under the conditions of the esterification step and which is beneficially readily separable from the taurine, as is already known in the art.
- the continuous esterification step 102 may, in respect of certain embodiments of using such a material for water removal, be initiated in advance of the introduction of the inert particulate material (or in advance of the initiation of contact with the inert particulate material by MEA, sulfuric acid or both) and then continued in the presence of the inert particulate material and with the associated water removal provided by the material, or in other embodiments, the inert particulate material can be introduced as either or both of monoethanolamine and sulfuric acid are provided to the esterification step 102 , for example, in the form of a slurry of sodium sulfate in MEA.
- a water removal step 104 whereby water is removed as the esterification step progresses can occur to a degree concurrent with the esterification step 102 as well as following the substantial completion of the esterification reaction and the formation of the 2-aminoethanol hydrogen sulfate ester intermediate, or can occur substantially concurrently with the esterification step 102 .
- the spray drying or thin film evaporation follows some reaction of monoethanolamine with sulfuric acid in the presence of the inert particulate material to form 2-aminoethanol hydrogen sulfate ester (in some upstream vessel as suggested by effluent 120 or even in the combining of monoethanolamine and sulfuric acid for spraying into a spray dryer via a nozzle which is amenable to the introduction of a liquid including an inert particulate solid), while in other embodiments the reaction of monoethanolamine with sulfuric acid in the presence of the inert particulate material will be carried out substantially in the spray dryer or thin film evaporator - in effect, carrying out esterification step 102 and water removal step 104 concurrently, and eliminating a separate effluent 120 from esterification step 102 .
- An example of the latter group of embodiments would involve spraying in (in the context of a spray dryer) or otherwise supplying (in the context of a thin film evaporator) the MEA and sulfuric acid separately - in certain embodiments including the inert particulate material such as sodium sulfate with the MEA or sulfuric acid to form a slurry which is sprayed into the spray dryer or supplied to the thin film evaporator.
- the inert particulate material in combination with any other water removal device or means removes enough water to enable full conversion to the desired 2-aminoethanol hydrogen sulfate ester intermediate in the form of effluent 122 , provide an AES intermediate that is free-flowing and not prone to fouling the walls of a spray dryer or downstream equipment leading to the sulfonation step as well as beneficially reduce water removal loads in the refining and purification of the finished taurine product, following the sulfonation step.
- effluent 122 comprising AES is then sent to a second, sulfonation step 106 , wherein the AES is continuously sulfonated by reaction with a sulfite, bisulfite or combination of these in the presence of carbon dioxide, a carbonate, bicarbonate or a combination of any of these in a second, sulfonation step to continuously produce a taurine product.
- the carbonate or bicarbonate may be any suitable carbonate or bicarbonate, such as soda ash.
- a convenient inexpensive salt such as sodium carbonate (Na2CO3) or sodium bicarbonate (NaHCO3) may be the source of carbonate/bicarbonate.
- Na2CO3 sodium carbonate
- NaHCO3 sodium bicarbonate
- Carbon dioxide as an alternative avoids the addition of an accompanying counterion that comes with the introduction of a carbonate or bicarbonate, and may be considered preferable for that reason by those of skill in the art.
- the aqueous solution of sulfite may in certain embodiments be sodium sulfite or sodium bisulfite.
- a base may be added to raise the pH of the reaction mixture to a range of about 7.0 to about 8.3.
- the base is chosen from an alkali metal hydroxide (e.g., sodium hydroxide) or ammonium hydroxide, or a combination thereof.
- a process comprises continuously adding a first stream, a second stream, and a third stream to a sulfonation vessel, wherein the first stream comprises AES, wherein the second stream comprises carbon dioxide, a carbonate, a bicarbonate or a combination of any of these, and wherein the third stream comprises an aqueous solution of a sulfite, bisulfite or combination of these.
- the process comprises continuously mixing the first, second and third streams in the sulfonation vessel, thus producing a mixture.
- the process comprises continuously subjecting the mixture to heat.
- the step of continuously subjecting the mixture to heat is performed in the presence of an inert gas.
- the process further comprises subjecting the mixture to a pressure greater than autogenous pressure.
- the 2-aminoethanol hydrogen sulfate ester (AES) has a residence time in the sulfonation vessel of no more than four (4) hours.
- the AES has a residence time in the sulfonation vessel of no more than two (2) hours, the heat is a temperature of 110-155° C., and the mixture is subjected to a pressure of at least 100 psi.
- the sulfite is chosen from at least one of a sulfite or a bisulfite, or combination thereof, e.g., sodium sulfite, sodium bisulfite, or combination thereof.
- the process results in a taurine yield of at least 80%.
- an advantage of adding the carbon dioxide, carbonate and/or bicarbonate to the reaction mixture of AES and sulfite and/or bisulfite is that the amount of sulfite and/or bisulfite required to obtain at least the same taurine yield in the same process is reduced as compared to that required in the absence of adding the carbon dioxide, carbonate and/or bicarbonate to the reaction mixture of AES and sulfite and/or bisulfite.
- the adding of the carbon dioxide, carbonate and/or bicarbonate to the reaction mixture of AES and sulfite reduces the mole ratio of sulfite to AES from about 1.8 and greater to about 1.2-1.3 to obtain at least the same taurine yield in the same process.
- the adding of the carbon dioxide, carbonate and/or bicarbonate to the reaction mixture of AES and sulfite and/or bisulfite reduces by about 28% the mole ratio of sulfite to AES required to obtain at least the same taurine yield in the same process but absent the carbon dioxide, carbonate and/or bicarbonate addition.
- the first stream comprised of AES and the second stream comprising carbon dioxide, a carbonate, a bicarbonate or a combination of any of these are mixed in a first part of the sulfonation vessel, with the third stream comprised of an aqueous solution of a sulfite, bisulfite or a combination thereof being mixed with the materials from the first part of the sulfonation vessel in a second part of the sulfonation vessel with heating to form taurine.
- a carbamate in addition to forming taurine, a carbamate may be formed.
- An example of carbamate is 2-(Carboxyamino)ethanesulfonic acid and is depicted in formula (ii) below.
- the carbamate in formula (ii) may be converted to taurine with the addition of an acid, such as concentrated sulfuric acid.
- pH adjustment e.g., by acidulation as just described
- pH adjustment in the sulfonation vessel provides increased taurine yield and less production of undesirable taurine by-products compared to carrying out the second, sulfonation step with no pH adjustment.
- the inert gas may be any suitable inert gas, including but not limited to nitrogen, helium, argon, and combinations thereof.
- the inert gas is nitrogen.
- the second, sulfonation step is conducted at a temperature of at least 115° C. and at a pressure greater than autogenous pressure. The presence of the inert gas subjects the mixture to the pressure greater than autogenous pressure.
- the sulfonation step is conducted at a pressure of at least 50 psi, more preferably at least 100 psi, and even more preferably at least 200 psi, and results in a taurine yield of at least 80%.
- At least a 95% AES conversion to taurine and a yield of at least 80% can be realized after a residence time of no more than four (4) hours in the vessel.
- This residence time of no more than four (4) hours is substantially less than the period of time normally required for sulfonation in conventional MEA methods.
- the AES has a residence time of no more than two (2) hours in the sulfonation vessel.
- sodium sulfate Na 2 SO 4
- esterification step 102 sodium sulfate may also be formed, which as mentioned previously can be recycled (typically in part compared to the overall amount of sodium sulfate formed) to the first, esterification step 102 for use as an inert particulate material having water removal capabilities.
- Sulfonation step 106 may comprise using an upflow or downflow sulfonation reactor wherein effluent 122 comprising AES is continuously pumped to the bottom or top of the sulfonation reactor, while a stream 124 comprising aqueous sodium sulfite, bisulfite or a combination is continuously supplied to the bottom or top of the sulfonation reactor and a stream 125 comprising one or more of carbon dioxide, a carbonate, e.g., soda ash, and a bicarbonate in water is continuously supplied to the bottom or top of the sulfonation reactor.
- the sulfonation reactor may be sealed with a pressure head with an inert gas 126 (e.g., nitrogen gas).
- Sulfonation step 106 comprises continuously subjecting the mixture of AES, sulfite and/or bisulfite, and carbon dioxide, carbonate and/or bicarbonate to heat in the presence of the inert gas.
- the heat may be a predetermined reaction temperature.
- the mixture of AES, sulfite or bisulfite, and carbon dioxide, carbonate and/or bicarbonate is continuously subjected to a pressure greater than autogenous pressure.
- the pressure may be at least 200 psi inert gas (e.g., nitrogen) and the reaction temperature maintained in the sulfonation vessel may be at least 115° C., in other embodiments being at least 120° C. up to 155° C.
- the sulfonation step may be carried out at from 140 to 155° C.
- Effluent 108 from sulfonation step 106 may then in certain embodiments be processed to remove the sodium sulfate, by means and methods known in the art.
- the insolubility of sodium sulfate in water lends itself, in particular, to a recovery of the sodium sulfate by precipitation, but other means may be conceived and used by those familiar with the manufacture of taurine and with the properties of sodium sulfate.
- the water of hydration acquired by the sodium sulfate in the esterification step 102 is then removed with heating for at least a recycle portion of the sodium sulfate, and the preferably anhydrous sodium sulfate in the recycle portion is then recycled back to the esterification step 102 .
- sodium sulfate is used as an inert particulate material in the esterification step 102
- sodium sulfite is understandably preferably recovered separately from the sodium sulfate, for example, by a chromatography step 110 .
- Effluent 112 from chromatography step 110 comprises taurine, and in certain embodiments the effluent 112 may be conveyed to crystallization step 114 to recover the taurine.
- the crystallization step 114 may comprise cooling effluent 112 from an elevated temperature, e.g., about 100° C., to a lower temperature, e.g., about 28° C.
- Crystallization step 114 may be preceded by a water removal step (not shown in FIG. 1 ) wherein further water is removed from effluent 112 , e.g., by distillation, thereby concentrating the amount of taurine in effluent 112 prior to crystallization.
- Effluent 116 from crystallization step 114 comprises crystallized taurine and may be conveyed to filtration step 118 .
- filtration step 118 crystallized taurine is separated from any unreacted AES.
- effluent 112 may in certain embodiments be conveyed directly to the filtration step 118 , with additional water removal again optionally preceding a cooling of the effluent 112 to cause the taurine to precipitate as a filterable mass from any unreacted AES from the sulfonation step 106 .
- FIG. 2 depicts a purely illustrative drying apparatus 200 for accomplishing an additional measure of water removal in certain embodiments of.
- Drying apparatus 200 comprises spray dryer 202 .
- Drying apparatus 200 comprises drying gas 204 .
- Drying gas 204 may be an inert gas, e.g., nitrogen.
- Liquid feed 206 may be the same as effluent 120 shown in FIG.
- a mixture of substantially unreacted monoethanolamine and sulfuric acid can be supplied directly to the spray dryer 202 (in an embodiment, with inert particulate material such as sodium sulfate being included in one or the other or both in a slurry form) or MEA, sulfuric acid or both may be independently supplied to the spray dryer in any manner known to those in the spray drying art - in co-current or countercurrent flows.
- Spray dryer 202 may comprise drying chamber 210 and an atomizer 208 configured to atomize a liquid feed 206 .
- Effluent 212 from spray dryer 202 may be conveyed to cyclone 214 .
- exhaust gas 216 is separated from effluent 222 .
- Effluent 222 exits cyclone 214 through opening 218 .
- Effluent 222 comprising unreacted AES, may be collected in a collector 220 .
- effluent 222 comprising AES has less water than liquid feed 206 .
- FIG. 3 depicts a particular apparatus 300 for sulfonation step 106 shown in FIG. 1 in accordance with aspects of the invention, using carbon dioxide, carbonate and/or bicarbonate addition in the sulfonation step 106 .
- apparatus 300 may comprise an upflow sulfonation reactor 302 .
- the sulfonation reactor may also be a downflow sulfonation reactor.
- Feed 304 in feed vessel 306 may be degassed by an inert gas prior to being conveyed out of feed vessel 306 .
- the inert gas may be any suitable inert gas, including but not limited to nitrogen, helium, argon, and combinations thereof.
- Feed 304 is continuously conveyed out of feed vessel 306 by pump 308 to bottom 310 of upflow sulfonation reactor 302 .
- Feed 304 may be the same as effluent 222 shown in FIG. 2 .
- feed 304 comprises AES.
- AES may be continuously pumped to the bottom of the sulfonation reactor 302 .
- AES reacts with sulfite and/or bisulfite present in the sulfonation reactor 302 to form taurine.
- Aqueous sulfite and/or bisulfite 322 e.g., aqueous sodium sulfite and/or aqueous sodium bisulfite, in vessel 324 may be degassed by an inert gas prior to being conveyed out of vessel 324 .
- the inert gas may be any suitable inert gas, including but not limited to nitrogen, helium, argon, and combinations thereof. In a preferred embodiment, the inert gas is nitrogen.
- Aqueous sulfite and/or bisulfite 322 is continuously conveyed out of vessel 324 as stream 326 by pump 328 to bottom 310 of upflow sulfonation reactor 302 .
- carbon dioxide, carbonate and/or bicarbonate stream 332 is continuously conveyed out of a source 334 of the carbon dioxide, carbonate and/or bicarbonate to the bottom 310 of upflow sulfonation reactor 302 .
- the source 334 can be any suitable carbon dioxide source, e.g., a pressurized tank of carbon dioxide, a compressor conveying carbon dioxide or a process stream of carbon dioxide,
- Sulfonation reactor 302 may be sealed with a pressure head with an inert gas, e.g., inert gas 330 .
- Sulfonation reactor 302 may be operated by heating the reaction mixture of AES and aqueous sulfite and/or bisulfite at a reaction temperature and under a reaction pressure, e.g., a reaction pressure of at least 200 psi inert gas (e.g., nitrogen).
- the reaction temperature may be at least 110° C.
- the reaction temperature may be at least 120° C.
- the reaction temperature may be 120 - 155° C.
- the reaction temperature may be 140 - 155° C.
- effluent 318 may be collected in vessel 320 .
- effluent 318 comprises taurine and may also comprise Na 2 SO 4 and Na 2 SO 3 .
- Exhaust gas 312 comprising inert gas may exit sulfonation reactor 302 through conduit 314 as may be desired, e.g., to purge materials in sulfonation reactor, or maintain a predetermined pressure in the sulfonation reactor 302 .
- FIG. 4 depicts an alternative sulfonation apparatus 400 for performing a sulfonation step 106 using carbon dioxide, carbonate and/or bicarbonate addition.
- Apparatus 400 is the same as apparatus 300 shown FIG. 3 , with the exception that aqueous sulfite and/or bisulfite stream 326 is continuously conveyed by pump 328 to an upper part 406 of upflow sulfonation reactor 302 through inlet 402 , rather than to the bottom 310 of upflow sulfonation reactor 302 .
- AES of feed 304 may react with carbon dioxide, carbonate and/or bicarbonate 332 to form a carbamate intermediate as previously mentioned, in lower part 404 of upflow sulfonation reactor 302 .
- lower part 404 is below dashed line A-A and upper part 406 is above dashed line A-A.
- aqueous sulfite and/or bisulfite of stream 326 reacts with materials from lower part 404 to form taurine.
- FIG. 5 depicts a process flow diagram of a continuous taurine production process in accordance with aspects of the invention.
- a continuous taurine manufacturing process 500 comprises providing a mixture 502 of AES and a sulfite and/or bisulfite and combining the same with stream 504 of carbon dioxide to form a sulfonation reaction mixture 506 , then conveying the mixture 506 to a reactor 508 wherein taurine 510 is continuously formed from the mixture 506 .
- Continuous reactor 508 may be the same as the sulfonation reactor 302 in FIGS. 3 and 4 , and may thus be an upflow or downflow reactor.
- An inert gas such as the inert gas 330 in FIG. 3 , may be conveyed to reactor 508 and subject the sulfonation reaction mixture 506 to a pressure equal to or greater the autogenous pressure of the reaction mixture 506 at the reaction temperature prevailing in the reactor 508 .
- Table 1 summarizes the differences in the sulfonation steps of our process as compared to a traditional or conventional MEA method not using carbon dioxide, carbonate and/or bicarbonate addition, according to our experience with our method and our experience with and understanding of a typical, traditional or conventional method.
- the undesirable taurine by-products include specifically N-2-aminoethyl-2-aminoethanesulfonic acid, which is seen in a conventional MEA process but which we have not detected in taurine produced according to our method.
- Table 2 shows the effect of various carbonate amounts on taurine yield from an illustrative second, sulfonation step conducted at 150° C. over the course of an hour under 100 psi of nitrogen, using a 1.3:1 molar ratio of sodium bisulfite to AES.
- Sodium hydroxide was added in the molar ratios shown in Table 2 to raise the pH of the reaction mixture to the pH values shown in Table 2.
- a 300 cc Hasteloy autoclave reactor was charged with 35 g of Na 2 SO 3 , 150 g water, and heated to 50° C. to dissolve Na 2 SO 3 . After dissolving Na 2 SO 3 in the water, 28 g of aminoethanol sulfate ester (AES) solid was added to autoclave reactor. The autoclave reactor was then sealed with a pressure head, purged three time with N 2 gas, then heated to 115° C. for sixteen (16) hours with 244 psi N 2 gas. After this time, the reaction was quenched by flash cooling in an ice bath. Once the thermocouple temperature read 20° C., the pressure head was removed, and liquid transferred to a storage vessel. The product was analyzed by LC and 1 H, C13 NMR. Results from these analyses indicated a 100% AES conversion with 85% taurine yield.
- AES aminoethanol sulfate ester
- a 300 cc Hasteloy autoclave reactor was charged with 35 g of Na 2 SO 3 , 150 g water, and heated to 50° C. to dissolve Na 2 SO 3 . After dissolving Na 2 SO 3 in the water, 28 g of aminoethanol sulfate ester (AES) solid was added to autoclave reactor. The autoclave reactor was then sealed with a pressure head, purged three time with N 2 gas, then heated to 115° C. for five (5) hours with 900 psi N 2 gas. After this time, the reaction was quenched by flash cooling in an ice bath. Once the thermocouple temperature read 20° C., the pressure head was removed, and liquid transferred to a storage vessel. The product was analyzed by LC and 1 H, C13 NMR. Results from these analyses indicated that an 86% AES conversion with 82% taurine yield.
- AES aminoethanol sulfate ester
- a 250 ml round bottom flask was charged with 18 g of Na 2 SO 3 , 75 g water, and heated to 50° C. to dissolve Na 2 SO 3 . After dissolving Na 2 SO 3 in the water, 14 g of aminoethanol sulfate ester (AES) solid was added to flask. The flask was refluxed at 115° C. for thirty (30) hours. After this time, the reaction was quenched by flash cooling in an ice bath. The product was analyzed by LC and 1 H, C13 NMR. Results from these analyses indicated a 73% AES conversion with 68% taurine yield.
- AES aminoethanol sulfate ester
- a 300 cc Hasteloy autoclave reactor was charged with 35 g of Na 2 SO 3 , 150 g water, and heated to 50° C. to dissolve Na 2 SO 3 . After dissolving Na 2 SO 3 in the water, 28 g of aminoethanol sulfate ester (AES) solid was added to reactor. The reactor was then sealed with a pressure head, purged three time with N 2 gas, then heated to 105° C. for six (6) hours with 200 psi N 2 gas. After this time, the reaction was quenched by flash cooling in an ice bath. Once the thermocouple temperature read 20° C., the pressure head was removed, and liquid transferred to a storage vessel. The product was analyzed by LC and 1 H, 13 C NMR. Results from these analyses indicated a 62% AES conversion with 58% taurine yield.
- AES aminoethanol sulfate ester
- a 300 cc Hasteloy autoclave reactor was charged with 35 g of Na 2 SO 3 , 150 g water, and heated to 50° C. to dissolve Na 2 SO 3 . After dissolving Na 2 SO 3 in the water, 28 g of aminoethanol sulfate ester (AES) solid was added to reactor. The reactor was then sealed with a pressure head, purged three time with N 2 gas, then heated to 115° C. for five (5) hours with 900 psi N 2 gas. After this time, the reaction was quenched by flash cooling in an ice bath. Once the thermocouple temperature read 20° C., the pressure head was removed, and liquid transferred to a storage vessel. The product was analyzed by LC and 1 H, 13 C NMR. Results from these analyses indicated an 86% AES conversion with 81% taurine yield.
- AES aminoethanol sulfate ester
- Example 3 had a sulfonation stage with a reaction time of thirty (30) hours and was not under pressure with N 2 gas.
- Examples 1, 2, 4, and 5, had much shorter sulfonation stages of either five (5) or (six) hours under pressure with N 2 gas.
- the following example demonstrates a method wherein a thin film evaporator is used to remove water.
- the thin film evaporator may be used for the water removal step 104 shown in FIG. 1 .
- MEA 20 g
- H 2 SO 4 36 g
- the reactor used for the water removal step was placed in an ice/water bath during the initial H 2 SO 4 addition to control the exothermic acid-base reaction.
- the following example demonstrates a method wherein a spray dryer is used to remove water.
- the spray dryer may be used for the water removal step 104 shown in FIG. 1 .
- reacting step 102 shown in FIG. 1 In accordance with reacting step 102 shown in FIG. 1 , In accordance with reacting step 102 shown in FIG. 1 , MEA (12 g) was charged into a 250 ml flask equipped with a stirrer and a thermometer. H 2 SO 4 (20 g) molar ratio (1:1) was slowly added into the flask over 30 minutes employing a dropping funnel.
- Monoethanolamine (MEA) and sulfuric acid were premixed at a 1:1 molar ratio by slowly adding concentrated sulfuric acid into MEA in an ice bath. 3 wt% of anhydrous sodium sulfate was added to the premixed MEA and sulfuric acid mixture. This mixture was then fed into the same spray dryer used in Example 7 through a peristaltic pump and a spray nozzle for the generation of 2-aminoethanol hydrogen sulfate ester (AES).
- AES 2-aminoethanol hydrogen sulfate ester
- the inlet temperature of the spray dryer instrument was approximately 190° C.
- the drying gas was set at a gas flow rate of 470 L/h.
- the flow rate of the feed to the spray dryer was about 1.5 mL/min.
- the aspirator output of the instrument was set at 100% for all the experiments.
- Monoethanolamine (MEA) and sulfuric acid were premixed at a 1:1 molar ratio by slowly adding concentrated sulfuric acid into the MEA in an ice bath. 3 wt% of anhydrous sodium sulfate was added to the premixed MEA and sulfuric acid mixture. This mixture was then fed into the spray dryer through a peristaltic pump and a spray nozzle for the generation of 2-aminoethanol hydrogen sulfate ester (AES).
- AES 2-aminoethanol hydrogen sulfate ester
- the inlet temperature of the spray dryer instrument was approximately 160° C.
- the drying gas was set at a gas flow rate of 470 L/h.
- the flow rate of the feed to the spray dryer was 1.5 mL/min.
- the aspirator output of the instrument was set at 100% for all the experiments.
- the generated 2-aminoethanol hydrogen sulfate ester (AES) was in the form of a more free flowing, less tacky white solid as compared to that obtained in Example 7.
- the product was then collected and analyzed by 1H NMR and UPLC, and the addition of sodium sulfate was thereby confirmed as enabling improved yields of a comparable purity AES product to that obtained under the same circumstances but absent the addition of the anhydrous sodium sulfate.
- the generated 2-aminoethanol hydrogen sulfate ester (AES) was in the form of a more free flowing, less tacky white solid as compared to that obtained in Example 7.
- the product was then collected and analyzed by 1H NMR and UPLC, and the addition of sodium sulfate was thereby confirmed as enabling improved yields of a comparable purity AES product to that obtained under the same circumstances but absent the addition of the anhydrous sodium sulfate.
- the generated 2-aminoethanol hydrogen sulfate ester (AES) was in the form of a more free flowing, less tacky white solid as compared to that obtained in Example 7.
- the product was then collected and analyzed by 1H NMR and UPLC, and the addition of sodium sulfate was thereby confirmed as enabling improved yields of a comparable purity AES product to that obtained under the same circumstances but absent the addition of the anhydrous sodium sulfate.
- 30 cc reactors were built with stainless steel with bodies and an internal diameter (ID) of 0.61 inches.
- the reactors are jacketed and are heated with circulating oil. Reactor temperatures are monitored via an internal thermowell 1 ⁇ 8′′ with a 1/16′′ thermocouple that can slide up and down to monitor peak temperature.
- the temperature of the jacket is monitored by measuring the oil temperature just before it enters the jacket.
- the temperatures of the reactors are controlled by adjusting the oil temperature.
- the inlets of the reactors are attached to an Isco dual piston pump and mass flow controllers for supplying gases.
- the outlet was attached to a condenser kept at 5° C. by a chiller unit.
- the pressures of the reactors are controlled using a dome loaded back pressure regulator (Mity Mite brand).
- a 5-gallon autoclave reactor was charged with 5.7 kg of 40% sodium bisulfite (NaHSO 3 ), and 2.26 kg of AES in 7.5 kg of water, then 975 grams of NaOH was added to above mixture with stirring. To above mixture, 616 grams of soda ash was added to keep the solution pH at 8.1. The reactor was then sealed with a pressure head, purged three times with nitrogen, then heated to 150° C. for 45 minutes (0.75 hours) with 200 psi nitrogen. After this time, the reaction was quenched by flash cooling in an ice bath. Once the thermocouple temperature read 20 deg. Celsius, the pressure head was removed, and liquid transferred to a storage vessel. The product was analyzed by LC-MS. Results from these indicated 100% AES conversion with 82% yield of taurine.
- Example 15 addition of an acid, e.g., concentrated sulfuric acid, to a mixture of taurine and carbamate will convert the carbamate to taurine.
- an acid e.g., concentrated sulfuric acid
- a similar addition of acid, such as concentrated sulfuric acid to the mixture of taurine and carbamate in Example 16, i.e., Samples 1-2, 4-13 and 15-43 made with carbonate (here, sodium carbonate) in accordance with aspects of the present invention, will convert the carbamate to taurine, resulting in a higher total taurine yield than without the addition of the carbonate.
- the control Samples 3 and 14 had a total taurine yield (molar) of 60.2 and 64.2, respectively.
- Samples 1-2, 4-13 and 15-43 made with carbonate in accordance with aspects of the present invention had higher total taurine yield (molar), with the exception of Sample 19.
- the total taurine yield of Sample 19 is due to the low molar ratio of sulfite/AES of 0.92% (sodium bisulfite/AES), whereas the control Samples 3 and 14 had higher molar ratio of sulfite/AES of 1.3% (sodium bisulfite/AES) and 1.29% (sodium sulfite/AES), respectively.
- Samples 4-13 and 15-28 all had yields of the taurine byproduct N-2-aminoethyl-2-aminoethane sulfonic acid (molar) that were much lower than control Sample 3 that had a yield of 23% (molar) of the same undesirable taurine byproduct.
- Control Sample 14 was not measured for N-2-aminoethyl-2-aminoethane sulfonic acid. However, in view of the results of control Sample 3, it would be expected that control Sample 14 would give similar results and much higher yields of the undesirable byproduct than seen in Samples 4-13 and 15-28.
- the MEA and 2-oxazolidinone in the product mixture may be recycled for upstream processing to yield more taurine.
- MEA can be recycled back to reacting step 102 of FIG. 1 for making AES from MEA.
- the 2-oxazolidinone in the product mixture may be recycled to the sulfonation reactor for production of taurine. Less than 1% of the N-2-aminoethyl-2-aminoethanesulfonic acid byproduct was formed.
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